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Zeitschrift für Naturforschung B

A Journal of Chemical Sciences

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Synthesis, crystal structure and properties of Cd(NCS)2 coordination compounds with two different Cd coordination modes

Aleksej Jochim
  • Institut für Anorganische Chemie, Christian-Albrechts-Universität zu Kiel, Max-Eyth-Straße 2, Kiel 24118, Germany
  • Other articles by this author:
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/ Gianpiero Gallo / Robert Dinnebier / Christian Näther
  • Corresponding author
  • Institut für Anorganische Chemie, Christian-Albrechts-Universität zu Kiel, Max-Eyth-Straße 2, Kiel 24118, Germany, Fax: +49-431-8801520
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Published Online: 2018-11-22 | DOI: https://doi.org/10.1515/znb-2018-0169

Abstract

Reaction of Cd(NCS)2 with 4-methoxypyridine leads to the formation of four new compounds, of which one crystallizes in two different polymorphs. In Cd(NCS)2(4-methoxypyridine)4·(4-methoxypyridine)2 (1) and Cd(NCS)2(4-methoxypyridine)4 (2-I and 2-II) discrete complexes are found, in which the Cd cations are octahedrally coordinated by four 4-methoxypyridine co-ligands and two terminally N-bonded thiocyanate anions. For the polymorphs 2-I and 2-II no single crystals are available and therefore, the corresponding Mn(II) compound (2-I-Mn) was prepared, which is isotypic to 2-I, as proven by a Rietveld refinement. The crystal structure of 2-II was solved and refined from XRPD data. In [Cd(NCS)2(4-methoxypyridine)2]n (3), the Cd cations are also octahedrally coordinated but linked into linear chains by pairs of thiocyanate anions with all ligands in trans-position. {[Cd(NCS)2]3(4-methoxypyridine)5}n (4) also consists of chains but two different Cd coordination modes are observed. Two of the three crystallographically independent Cd cations show an octahedral coordination with a trans- or cis-arrangement of the N and S atoms of the anionic ligands, whereas the third one is in a distorted square-pyramidal coordination, with cis-coordination of the thiocyanate N and S atoms. Measurements using simultaneous thermogravimetry and differential scanning calorimetry of 2-I and 2-II show different heating rate dependent mass steps, in which the co-ligands are removed. In some of the residues obtained after the respective TG steps compound 3 was detected but no phase pure samples could be obtained.

Keywords: 4-methoxypyridine; 5- and 6-fold coordination; Cd(NCS)2 coordination compounds; crystal structures; thermal properties

Dedicated to: Professor Wolfgang Bensch on the occasion of his 65th birthday.

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About the article

Received: 2018-08-15

Accepted: 2018-10-20

Published Online: 2018-11-22


Funding Source: Deutsche Forschungsgemeinschaft

Award identifier / Grant number: Na 720/5-2

This project was supported by the Deutsche Forschungsgemeinschaft (Project No. Na 720/5-2) and the State of Schleswig-Holstein. We thank Prof. Dr. Wolfgang Bensch for access to his experimental facilities.


Citation Information: Zeitschrift für Naturforschung B, 20180169, ISSN (Online) 1865-7117, ISSN (Print) 0932-0776, DOI: https://doi.org/10.1515/znb-2018-0169.

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